Chemical-mechanical planarization composition having PVNO and associated method for use

ABSTRACT

A composition and associated method for chemical mechanical planarization (or other polishing) are described. The composition comprises an abrasive and a polyvinylpyridine-N-oxide polymer. The composition possesses high selectivities for metal and barrier material removal in metal CMP. The composition may further comprise an oxidizing agent in which case the composition is particularly useful in conjunction with the associated method for metal CMP applications (e.g., copper CMP).

BACKGROUND OF THE INVENTION

This invention relates generally to the chemical-mechanical polishing (CMP) of metal substrates on semiconductor wafers and slurry compositions therefor. In particular, the present invention relates to a CMP slurry composition which is characterized to possess high selectivities for removal of metal and barrier material in relation to dielectric material during CMP processing of substrates comprised of metal, barrier material, and dielectric material. This invention is especially useful for copper CMP and most especially for copper CMP step 2.

Chemical mechanical planarization (chemical mechanical polishing, CMP) for planarization of semiconductor substrates is now widely known to those skilled in the art and has been described in numerous patents and open literature publications. Some introductory references on CMP are as follows: “Polishing Surfaces for Integrated Circuits”, by B. L. Mueller and J. S. Steckenrider, Chemtech, February, 1998, pages 38-46; and H. Landis et al., Thin Solids Films, 220 (1992), page 1.

In a typical CMP process, a substrate (e.g., a wafer) is placed in contact with a rotating polishing pad attached to a platen. A CMP slurry, typically an abrasive and chemically reactive mixture, is supplied to the pad during CMP processing of the substrate. During the CMP process, the pad (fixed to the platen) and substrate are rotated while a wafer carrier system or polishing head applies pressure (downward force) against the substrate. The slurry accomplishes the planarization (polishing) process by chemically and mechanically interacting with the substrate film being planarized due to the effect of the rotational movement of the pad relative to the substrate. Polishing is continued in this manner until the desired film on the substrate is removed with the usual objective being to effectively planarize the substrate. Typically metal CMP slurries contain an abrasive material, such as silica or alumina, suspended in an oxidizing, aqueous medium.

Silicon based semiconductor devices, such as integrated circuits (ICs), typically include a silicon dioxide dielectric layer. Multilevel circuit traces, typically formed from aluminum or an aluminum alloy or copper, are patterned onto the silicon dioxide substrate.

CMP processing is often employed to remove and planarize excess metal at different stages of semiconductor manufacturing. For example, one way to fabricate a multilevel copper interconnect or planar copper circuit traces on a silicon dioxide substrate is referred to as the damascene process. In a semiconductor manufacturing process typically used to form a multilevel copper interconnect, metallized copper lines or copper vias are formed by electrochemical metal deposition followed by copper CMP processing. In a typical process, the interlevel dielectric (ILD) surface is patterned by a conventional dry etch process to form vias and trenches for vertical and horizontal interconnects and make connection to the sublayer interconnect structures. The patterned ILD surface is coated with an adhesion-promoting layer such as titanium or tantalum and/or a diffusion barrier layer such as titanium nitride or tantalum nitride over the ILD surface and into the etched trenches and vias. The adhesion-promoting layer and/or the diffusion barrier layer is then overcoated with copper, for example, by a seed copper layer and followed by an electrochemically deposited copper layer. Electro-deposition is continued until the structures are filled with the deposited metal. Finally, CMP processing is used to remove the copper overlayer, adhesion-promoting layer, and/or diffusion barrier layer, until a planarized surface with exposed elevated portions of the dielectric (silicon dioxide and/or low-k) surface is obtained. The vias and trenches remain filled with electrically conductive copper forming the circuit interconnects.

When one-step copper CMP processing is desired, it is usually important that the removal rate of the metal and barrier layer material be significantly higher than the removal rate for dielectric material in order to avoid or minimize dishing of metal features or erosion of the dielectric. Alternatively, a multi-step copper CMP process may be employed involving the initial removal and planarization of the copper overburden, referred to as a step 1 copper CMP process, followed by a barrier layer CMP process. The barrier layer CMP process is frequently referred to as a barrier or step 2 copper CMP process. Previously, it was believed that the removal rate of the copper and the adhesion-promoting layer and/or the diffusion barrier layer must both greatly exceed the removal rate of dielectric so that polishing effectively stops when elevated portions of the dielectric are exposed. The ratio of the removal rate of copper to the removal rate of dielectric base is called the “selectivity” for removal of copper in relation to dielectric during CMP processing of substrates comprised of copper, tantalum and dielectric material. The ratio of the removal rate of copper to the removal rate of tantalum is called the “selectivity” for removal of copper in relation to tantalum during CMP processing. When CMP slurries with high selectivity for removal of copper and tantalum in relation to dielectric are used, the copper layers are easily over-polished creating a depression or “dishing” effect in the copper vias and trenches. This feature distortion is unacceptable due to lithographic and other constraints in semiconductor manufacturing.

Another feature distortion that is unsuitable for semiconductor manufacturing is called “erosion.” Erosion is the topography difference between a field of dielectric and a dense array of copper vias or trenches. In CMP, the materials in the dense array maybe removed or eroded at a faster rate than the surrounding field of dielectric. This causes a topography difference between the field of dielectric and the dense copper array.

A typically used CMP slurry has two actions, a chemical component and a mechanical component. An important consideration in slurry selection is “passive etch rate.” The passive etch rate is the rate at which copper is dissolved by the chemical component alone and should be significantly lower than the removal rate when both the chemical component and the mechanical component are involved. A large passive etch rate leads to dishing of the copper trenches and copper vias, and thus, preferably, the passive etch rate is less than 10 nanometers per minute.

A number of systems for CMP of copper have been disclosed. A few illustrative examples are listed next Kumar et al. in an article entitled “Chemical-Mechanical Polishing of Copper in Glycerol Based Slurries” (Materials Research Society Symposium Proceedings, 1996) disclose a slurry that contains glycerol and abrasive alumina particles. An article by Gutmann et al. entitled “Chemical-Mechanical Polishing of Copper with Oxide and Polymer Interlevel Dielectrics” (Thin Solid Films, 1995) discloses slurries based on either ammonium hydroxide or nitric acid that may contain benzotriazole (BTA) as an inhibitor of copper dissolution. Luo et al. in an article entitled “Stabilization of Alumina Slurry for Chemical-Mechanical Polishing of Copper” (Langmuir, 1996) discloses alumina-ferric nitrate slurries that contain polymeric surfactants and BTA. Carpio et al. in an article entitled “Initial Study on Copper CMP Slurry Chemistries” (Thin Solid Films, 1995) disclose slurries that contain either alumina or silicon particles, nitric acid or ammonium hydroxide, with hydrogen peroxide or potassium permanganate as an oxidizer.

In relation to copper CMP, the current state of this technology involves use of a two-step process to achieve local and global planarization in the production of IC chips. During step 1 of a copper CMP process, the overburden copper is removed. Then step 2 of the copper CMP process follows to remove the barrier layer and achieve both local and global planarization. Generally, after removal of overburden copper in step 1, polished wafer surfaces have non-uniform local and global planarity due to differences in the step heights at various locations of the wafer surfaces. Low density features tend to have higher copper step heights whereas high density features tend to have low step heights. Due to differences in the step heights after step 1, step 2 copper CMP selective slurries with respect to tantalum to copper removal rates and copper to oxide removal rates are highly desirable. The ratio of the removal rate of tantalum to the removal rate of copper is called the “selectivity” for removal of tantalum in relation to copper during CMP processing of substrates comprised of copper, tantalum and dielectric material.

There are a number of theories as to the mechanism for chemical-mechanical polishing of copper. An article by Zeidler et al. (Microelectronic Engineering, 1997) proposes that the chemical component forms a passivation layer on the copper changing the copper to a copper oxide. The copper oxide has different mechanical properties, such as density and hardness, than metallic copper and passivation changes the polishing rate of the abrasive portion. The above article by Gutmann et al. discloses that the mechanical component abrades elevated portions of copper and the chemical component then dissolves the abraded material. The chemical component also passivates recessed copper areas minimizing dissolution of those portions.

These are two general types of layers that can be polished. The first layer is interlayer dielectrics (ILD), such as silicon oxide and silicon nitride. The second layer is metal layers such as tungsten, copper, aluminum, etc., which are used to connect the active devices.

In the case of CMP of metals, the chemical action is generally considered to take one of two forms. In the first mechanism, the chemicals in the solution react with the metal layer to continuously form an oxide layer on the surface of the metal. This generally requires the addition of an oxidizer to the solution such as hydrogen peroxide, ferric nitrate, etc. Then the mechanical abrasive action of the particles continuously and simultaneously removes this oxide layer. A judicious balance of these two processes obtains optimum results in terms of removal rate and polished surface quality.

In the second mechanism, no protective oxide layer is formed. Instead, the constituents in the solution chemically attack and dissolve the metal, while the mechanical action is largely one of mechanically enhancing the dissolution rate by such processes as continuously exposing more surface area to chemical attack, raising the local temperature (which increases the dissolution rate) by the friction between the particles and the metal and enhancing the diffusion of reactants and products to and away from the surface by mixing and by reducing the thickness of the boundary layer.

While prior art CMP systems are capable of removing a copper overlayer from a silicon dioxide substrate, the systems do not satisfy the rigorous demands of the semiconductor industry. These requirements can be summarized as follows. First, there is a need for high removal rates of copper to satisfy throughput demands. Secondly, there must be excellent topography uniformity across the substrate. Finally, the CMP method must minimize local dishing and erosion effects to satisfy ever increasing lithographic demands.

BRIEF SUMMARY OF THE INVENTION

In one embodiment, the invention is a polishing composition comprising:

-   -   a) an abrasive; and     -   b) a polyvinylpyridine-N-oxide polymer.

The polishing composition is useful in chemical-mechanical polishing (CMP), especially in metal CMP.

In another embodiment, the invention is a method of polishing comprising the steps of:

-   -   A) placing a substrate in contact with a polishing pad;     -   B) delivering a polishing composition comprising a) an abrasive;         and a polyvinylpyridine-N-oxide polymer; and     -   C) polishing the substrate with the polishing composition.

DETAILED DESCRIPTION OF THE INVENTION

It has been found that CMP polishing compositions comprising an abrasive and a polyvinylpyridine-N-oxide possess high selectivities for metal and barrier material (e.g., tantalum) removal in relation to dielectric (e.g., PETEOS or TEOS) removal during CMP processing.

The high metal to dielectric material and /or barrier material to dielectric material selective CMP slurry of this invention comprises a) an abrasive and b) a polyvinylpyridine-N-oxide polymer. For metal CMP applications, the stable CMP slurry further comprises c) an oxidizing agent. Optionally, other additives may be included.

Both standard (unmodified) abrasives and organometallic-modified abrasives can be employed in this invention. Suitable unmodified abrasives include, but are not limited to, silica, alumina, titania, zirconia, germania, ceria, and co-formed products thereof, and mixtures thereof. An organometallic-modified abrasive obtained by treatment of an unmodified abrasive (e.g., silica) with an organometallic compound can also be employed in this invention. Suitable organometallic compounds for modification include aluminum acetate, aluminum formate, and aluminum propionate. Suitable abrasives include, but are not limited to, colloidal products, fumed products, and mixtures thereof.

Silica or organometallic-modified silica is a preferred abrasive material used in the present invention. The silica may be, for example, colloidal silica, fumed silica and other silica dispersions; however, the preferred silica is colloidal silica.

The abrasive is present in the slurry in a concentration of about 0.5 weight % to about 20 weight % of the total weight of the slurry. More preferably, the abrasive is present in a concentration of about 4 weight % to about 17 weight % of the total weight of the slurry. Most preferably, the abrasive is present in a concentration of about 4 weight % to about 15 weight % of the total weight of the slurry.

The polyvinylpyridine-N-oxide polymer in this invention can be unsubstituted (i.e., this being the parent polymer) or substituted with one or more substituents. Suitable substituents include, but are not limited to, hydroxyl, fluoro, chloro, bromo, iodo, amino, carboxylic, amido, ester, and alkoxy functional groups. In addition to the homopolymer polyvinylpyridine-N-oxide, the polymer in this invention can also be a copolymer or block copolymer of polyvinylpyridine-N-oxide with another polymer, such as polyvinylpyridine. The level of polyvinylpyridine-N-oxide polymer in the compositions of this invention can preferably range from about 0.02 weight % to about 1 weight %, more preferably range from about 0.05 weight % to about 0.35 weight %, and most preferably range from about 0.1 weight % to about 0.35 weight %.

The molecular weight of the polyvinylpyridine-N-oxide polymer in this invention is not limited but generally ranges, as a number average molecular weight, from about 1,000 to about 1 million. Preferably, the number average molecular weight ranges from about 25,000 Daltons to about 250,000 Daltons and more preferably is about 50,000 Daltons. Oligomers and low molecular weight polymers are included within the broad definition of the polyvinylpyridine-N-oxide polymer in this invention.

In embodiments of this invention having an oxidizing agent, the oxidizing agent can be any suitable oxidizing agent. Suitable oxidizing agents include, for example, one or more per-compounds, which comprise at least one peroxy group (—O—O—). Suitable per-compounds include, for example, peroxides, persulfates (e.g., monopersulfates and dipersulfates), percarbonates, and acids thereof, and salts thereof, and mixtures thereof. Other suitable oxidizing agents include, for example, oxidized halides (e.g., chlorates, bromates, iodates, perchlorates, perbromates, periodates, and acids thereof, and mixtures thereof, and the like), perboric acid, perborates, percarbonates, peroxyacids (e.g., peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, salts thereof, mixtures thereof, and the like), permanganates, chromates, cerium compounds, ferricyanides (e.g., potassium ferricyanide), mixtures thereof, and the like. Preferred oxidizing agents include, for example, hydrogen peroxide, urea-hydrogen peroxide, sodium peroxide, benzyl peroxide, di-t-butyl peroxide, peracetic acid, monopersulfuric acid, dipersulfuric acid, iodic acid, and salts thereof, and mixtures thereof.

In compositions of this invention directed to metal CMP, (hydrogen peroxide) H₂O₂ is used as a preferred oxidizing agent. Preferably the concentration of the H₂O₂ is from about 0.2 weight % to about 6 weight % of the total weight of the slurry.

Other chemicals that may be added to the CMP slurry composition include, for example, pH adjusting agents, surfactants, acids, corrosion inhibitors, fluorine-containing compounds, chelating agents, non-polymeric nitrogen-containing compounds, and salts.

Suitable surfactant compounds that may be added to the slurry composition include, for example, any of the numerous nonionic, anionic, cationic or amphoteric surfactants known to those skilled in the art. The surfactant compounds may be present in the slurry composition in a concentration of about 0 weight % to about 1 weight %, preferably about 0.0005 weight % to about 1 weight % and, more preferably in a concentration of about 0.001 weight % to about 0.5 weight % of the total weight of the slurry. The preferred types of surfactants are nonionic, anionic, or mixtures thereof and are most preferably present in a concentration of about 10 ppm to about 1000 ppm of the total weight of the slurry. Nonionic surfactants are most preferred. A preferred nonionic surfactant is Surfynol® 104E, which is 2,4,7,9-tetramethyl-5-decyn-4,7-diol, (Air Products and Chemicals, Allentown, Pa.).

The pH-adjusting agent is used to improve the stability of the polishing composition, to improve the safety in use or to meet the requirements of various regulations. As a pH-adjusting agent to be used to lower the pH of the polishing composition of the present invention, hydrochloric acid, nitric acid, sulfuric acid, chloroacetic acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids may be employed. On the other hand, as a pH-adjusting agent to be used for the purpose of raising the pH, potassium hydroxide, sodium hydroxide, ammonia, tetramethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, etc., may be employed. The polishing composition of the present invention is not particularly limited with respect to the pH, but it is usually adjusted to pH 3 to 10.

In metal CMP applications, compositions having acidic or neutral pH values are generally preferred according to this invention. In this case, a suitable slurry pH is from about 3 to about 10, preferably from about 5 to about 9.8, and more preferably, from about 7.5 to about 9.

Other suitable acid compounds that may be added (in place of or in addition to the pH-adjusting acids mentioned supra) to the slurry composition include, but are not limited to, formic acid, acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, lactic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, malic acid, tartaric acid, gluconic acid, citric acid, phthalic acid, pyrocatechoic acid, pyrogallol carboxylic acid, gallic acid, tannic acid, and mixtures thereof. These acid compounds may be present in the slurry composition in a concentration of about 0 weight % to about 5 weight % of the total weight of the slurry.

Suitable corrosion inhibitors that may be added to the slurry composition include, for example, benzotriazole, 6-tolylytriazole, tolyltriazole derivatives, 1-(2,3-dicarboxypropyl)benzotriazole, N-acyl-N-hydrocarbonoxyalkyl aspartic acid compounds, and mixtures thereof. The corrosion inhibitor may be present in the slurry in a concentration of about 0 ppm to about 4000 ppm, preferably from about 10 ppm to about 4000 ppm, and more preferably from about 50 ppm to about 200 ppm of the total weight of the slurry. Two preferred corrosion inhibitors are CDX2128 and CDX2165, both supplied by King Industries, which are preferably present in a concentration of about 50 ppm to about 1000 ppm of the total weight of the slurry.

Carboxylic acids, if added, may also impart corrosion inhibition properties to the slurry composition.

To increase the selectivity of tantalum and tantalum compounds relative to silicon dioxide, fluorine-containing compounds may be added to the slurry composition. Suitable fluorine-containing compounds include, for example, hydrogen fluoride, perfluoric acid, alkali metal fluoride salt, alkaline earth metal fluoride salt, ammonium fluoride, tetramethylammonium fluoride, ammonium bifluoride, ethylenediammonium difluoride, diethylenetriammonium trifluoride, and mixtures thereof. The fluorine-containing compounds may be present in the slurry composition in a concentration of about 0 weight % to about 5 weight %, preferably from about 0.65 weight % to about 5 weight %, and more from about 0.50 weight % to about 2.0 weight % of the total weight of the slurry. A preferred fluorine-containing compound is ammonium fluoride, which is preferably present in a concentration from about 0.45 weight % to about 1.0 weight % of the total weight of the slurry.

Suitable chelating agents that may be added to the slurry composition include, for example, ethylenediaminetetracetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid (NHEDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentacetic acid (DPTA), ethanoldiglycinate, and mixtures thereof. The chelating agents may be present in the slurry composition in a concentration of about 0 weight % to about 3 weight %, preferably from about 0.02 weight % to about 3 weight %, and more preferably from about 0.05 weight % to about 2.0 weight % of the total weight of the slurry.

Suitable non-polymeric nitrogen-containing compounds (amines, hydroxides, etc.) that may be added to the slurry composition include, for example, ammonium hydroxide, hydroxylamine, monoethanolamine, diethanolamine, triethanolamine, diethyleneglycolamine, N-hydroxylethylpiperazine, and mixtures thereof. These non-polymeric nitrogen-containing compounds may be present in the slurry composition in a concentration of about 0 weight % to about 1 weight %, and, if present, are normally present at a level of about 0.01 weight % to about 0.20 weight % of the total weight of the slurry. A preferred non-polymeric nitrogen-containing compound is ammonium hydroxide and is most preferably present in a concentration of about 0.01 weight % to about 0.1 weight % of the total weight of the slurry.

Suitable salts that optionally may be added to the slurry composition include, for example, ammonium persulfate, potassium persulfate, potassium sulfite, potassium carbonate, ammonium nitrate, potassium hydrogen phthalate, hydroxylamine sulfate, and mixtures thereof. The salts may be present in the slurry composition in a concentration of about 0 weight % to about 10 weight %, and, if present, are normally present at a level of about 0.02 weight % to about 5 weight % of the total weight of the slurry.

Still other chemicals that can be added to the slurry compositions are biological agents such as bactericides, biocides and fungicides especially if the pH is around about 6 to 9. Suitable biocides, include, but are not limited to, 1,2-benzisothiazolin-3-one; 2(hydroxymethyl)amino ethanol; 1,3-dihydroxymethyl-5,5-dimethylhydantoin; 1-hydroxymethyl-5,5-dimethylhydantion; 3-iodo-2-propynyl-butylcarbamate; glutaraldehyde; 1,2-dibromo-2,4-dicyanobutane; 5-chloro-2-methyl-4-isothiazoline-3-one; 2-methyl-4-isothiazolin-3-one; and mixtures thereof.

Associated Methods

The associated methods of this invention entail use of the aforementioned composition (as disclosed supra) for chemical mechanical planarization of substrates comprised of metals and dielectric materials. In the methods, a substrate (e.g., a wafer) is placed face-down on a polishing pad which is fixedly attached to a rotatable platen of a CMP polisher. In this manner, the substrate to be polished and planarized is placed in direct contact with the polishing pad. A wafer carrier system or polishing head is used to hold the substrate in place and to apply a downward pressure against the backside of the substrate during CMP processing while the platen and the substrate are rotated. The polishing composition (slurry) is applied (usually continuously) on the pad during CMP processing to effect the removal of material to planarize the substrate.

The composition and associated methods of this invention are effective for CMP of a wide variety of substrates, including substrates having dielectric portions that comprise materials having dielectric constants less than 3.3 (low-k materials). Suitable low-k films in substrates include, but are not limited to, organic polymers, carbon-doped oxides, fluorinated silicon glass (FSG), inorganic porous oxide-like materials, and hybrid organic-inorganic materials. Representative low-k materials and deposition methods for these materials are summarized below. Deposition Vendor Trade Name Method Material Air Products and MesoElk ® Spin-on Hybrid organic- Chemicals inorganic Applied Materials Black Diamond CVD Carbon-doped oxide Dow Chemical SiLK ™, Porous Spin-on Organic polymer SiLK ™ Honeywell NANOGLASS ® E Spin-on Inorganic oxide-like Electronic Materials Novellus Systems CORAL ® PECVD Carbon-doped oxide PECVD = Plasma enhanced chemical vapor deposition CVD = chemical vapor deposition

Similarly, the composition and associated methods of this invention are effective for CMP of substrates comprised of various metals, including, but not limited to, tantalum, titanium, tungsten and copper. The composition and associated methods of this invention are particularly useful and preferred for tungsten CMP and afford very high selectivities for removal of tungsten in relation to dielectric (as illustrated in the examples).

While not being bound by any particular theory, the inventor(s) believes that the following considerations may explain why a polishing composition comprising a) an abrasive and b) a polyvinylpyridine-N-oxide, abbreviated as PVNO, polymer exhibits high metal to dielectric selectivity in CMP processing. Under basic polishing conditions in a step 2 slurry, a dielectric layer (e.g., PETEOS, TEOS or low-K dielectric) develops a negative charge, which drives the counter positive ions (e.g., ammonium ions in the examples below as the pH was adjusted with ammonium hydroxide) to self-assemble on the dielectric surface. The oxygen attached to the aromatic nitrogen in the six-membered ring of the PVNO molecule attaches itself to the ionic double layer of the dielectric layer, thus protecting the dielectric oxide layer.

The present invention is further demonstrated by the examples below. GLOSSARY COMPONENTS BA CS Boric acid-modified colloidal silica CS Syton ® HT-50 (DuPont Air Products NanoMaterials L.L.C., Carlsbad, CA) colloidal silica CDX2128 Corrosion inhibitor - a water soluble amino acid derivative (King Industries, Inc., Norwalk, CT) CDX2165 Corrosion inhibitor - a triazole derivative (King Industries, Inc., Norwalk, CT) S104E Surfynol ® 104E - a 50:50 mixture by weight of 2,4,7,9-tetramethyl- 5-decyn-4,7-diol and ethylene glycol (solvent), Air Products and Chemicals, Allentown, PA. PETEOS Plasma enhanced deposition of tetraethoxy silane; a dielectric oxide layer. Politex ® Pad Polishing pad used during CMP, supplied by Rodel, Inc, Phoenix, AZ. PVNO Polyvinylpyridine-N-oxide (Reilly Industries, Inc., 300 North Meridian Street, Suite 1500, Indianapolis, Indiana, 46204.) CAS # 58984-27-3 TEOS Tetraethyl orthosilicate PARAMETERS General Å: angstrom(s) - a unit of length BP: back pressure, in psi units CMP: chemical mechanical planarization = chemical mechanical polishing CS: carrier speed DF: Down force: pressure applied during CMP; units psi min: minute(s) ml: milliliter(s) mV: millivolt(s) psi: pounds per square inch PS: platen rotational speed of polishing tool, in rpm (revolution(s) per minute) SF: slurry flow, ml/min Removal Rates Cu RR 4.5 psi Measured copper removal rate at 4.5 psi down pressure of the CMP tool Cu RR 2 psi Measured copper removal rate at 2 psi down pressure of the CMP tool PETEOS Measured PETEOS removal rate at 2 psi down pressure of the RR 2 psi CMP tool Ta RR 2 psi Measured tantalum removal rate at 2 psi down pressure of the CMP tool TEOS RR 2 psi Measured TEOS removal rate at 2 psi down pressure of the CMP tool Ta: Cu Sel Tantalum: Copper Selectivity - the ratio of the amount of tantalum removed to the amount of copper removed during CMP experiments under identical conditions. TEOS (or TEOS (or PETEOS): Copper Selectivity - The ratio of the amount PETEOS): of TEOS (or PETEOS) (dielectric material) removed to the amount Cu Sel of copper removed during CMP experiments under identical conditions.

EXAMPLES

General

All percentages are weight percentages and all temperatures are degrees Centigrade unless otherwise indicated.

CMP Methodology

In the examples presented below, CMP experiments were run using the procedures and experimental conditions given below.

Metrology

PETEOS thickness was measured with a Nanometrics, model, #9200, manufactured by Nanometrics Inc., 1550 Buckeye, Milpitas, Calif. 95035-7418. The metal films were measured with a ResiMap CDE, model 168, manufactured by Creative Design Engineering, Inc, 20565 Alves Dr, Cupertino, Calif., 95014. This tool is a four-point probe sheet resistance tool. Twenty-five and forty nine-point polar scans were taken with the respective tools at 3-mm edge exclusion.

CMP Tool

The CMP tool that was used is a Mirra®, manufactured by Applied Materials, 3050 Boweres Avenue, Santa Clara, Calif., 95054. A Rodel Politex® embossed pad, supplied by Rodel, Inc, 3804 East Watkins Street, Phoenix, Ariz., 85034, was used on the platen for the blanket wafer polishing studies. Pads were broken-in by polishing twenty-five dummy oxide (deposited by plasma enhanced CVD from a TEOS precursor, PETEOS) wafers. In order to qualify the tool settings and the pad break-in, two PETEOS monitors were polished with Syton®OX—K colloidal silica, supplied by DuPont Air Products NanoMaterials L.L.C., at baseline conditions.

In blanket wafers studies, groupings were made to simulate successive film removal: first copper, next tantalum, and finally the PETEOS. The tool mid-point conditions were: table speed; 123 rpm, head speed; 112 rpm, membrane pressure, 2.0 psi; inter-tube pressure, 0.0 psi; slurry flow, 200 ml/min.

Wafers

Polishing experiments were conducted using electrochemically deposited copper, tantalum, and PETEOS wafers. These blanket wafers were purchased from Silicon Valley Microelectronics, 1150 Campbell Ave CA 95126. The film thickness specifications are summarized below:

-   -   PETEOS: 15000 Å on silicon     -   Copper: 10,000 Å electroplated copper/1,000 Å copper seed/250 Å         tantalum on silicon     -   Tantalum: 2000 Å/5,000 Å thermal oxide on silicon     -   Zeta Potential Measurements

Zeta potential measurements were made using a Colloidal Dynamics instrument, manufactured by Colloidal Dynamics Corporation, 11-Knight Street, Building E8, Warwick, R.I. 02886. This instrument measures the zeta potential (surface charge) of colloidal particles, such as surface-modified colloidal silica particles of boric acid-modified colloidal silica.

Preparation of Boric Acid-Modified Colloidal Silica (BA CS)

Boric acid-modified colloidal silica having an average particle diameter of 40 to 55 nanometers was prepared using the following procedure:

Approximately 1 kg of Amberlite® IR-120 ion exchange resin (Rohm and Haas Company, Philadelphia, Pa.) was washed with 1 liter of 20% sulfuric acid solution. The mixture was stirred and the resin was allowed to settle. The aqueous layer was decanted and washed with 10 liters of deionized water. The mixture was again allowed to settle and then the aqueous layer was decanted. This procedure was repeated until the decanted water was colorless. This procedure afforded acid-state resin.

Syton® HT-50 (12 kg, approximately 2.27 gallons, DuPont Air Products NanoMaterials LLC, Carlsbad, Calif.) was placed in a 5 gallon mix tank equipped with an agitator. 2.502 kg of deionized water was added to the tank and the solution was allowed to mix a few minutes. The pH of the solution was measured to be approximately 10.2. With continued pH monitoring, small amounts of acid-state resin were added, while allowing the pH to stabilize in between additions. Additional resin was added in small portions until the pH had dropped to pH 1.90-2.20. Once this pH limit had been reached and was stable in this range, no further resin additions were made and the mixture was stirred for 1-1.5 hours. Subsequently the mixture was passed through a 500-mesh screen to remove the resin and afforded deionized Syton® HT-50.

A solution of 268 g of boric acid powder (Fisher Scientific, 2000 Park Lane, Pittsburgh, Pa., 15275) in 5.55 kg of deionized water was prepared in a 10 gallon mixing tank equipped with an agitator and a heater by slowly adding the boric acid powder until all had been added to the water and then agitating the mixture for 15 hours and increasing the temperature of the mixture to 55-65° C. Deionized, and diluted Syton® HT-50 (14.5 kg) was then added to the boric acid solution slowly over about 1.2 hours by adding it at approximately 200 ml/minute and maintaining the temperature greater than 52° C. while agitating the mixture. After this addition was completed, heating at 60° C. and agitation of the mixture was continued for 5.5 hours. The resulting solution was subsequently filtered through a 1-micron filter to afford boron surface-modified colloidal silica.

This boron surface-modified colloidal silica was characterized for colloid stability over 15 days using a Colloidal Dynamics instrument (11-Knight Street, Building E8,Warwick, R.I., 02886). This boron surface-modified colloidal silica was found to exhibit both constant pH (pH=˜6.6) and zeta potential (zp) (zp=˜−58 millivolts) over the 15-day test period. The percentage of surface sites of this surface-modified colloidal silica occupied by boron-containing compound(s) was approximately 98%.

Examples 1-4

In these examples, CMP slurry compositions as shown in Table 1 were prepared and tested using the methodology, equipment, and processing as described supra. These CMP slurry compositions were comprised of PVNO, boric acid-modified colloidal silica, ammonium fluoride, Surfynol® 104E, hydrogen peroxide, CDX2128, and ammonium hydroxide in an aqueous medium at pH 8. pH adjustment was done using ammonium hydroxide. The CMP slurry component amounts are shown in Table 1 for these examples. In each case, the balance of the composition was deionized water.

In these examples, the level of PVNO was varied as indicated below (and in Table 1):

-   -   Example 1—Table 1, PVNO level=0.25 wt. %     -   Example 2—Table 1, PVNO level=0.125 wt. %     -   Example 3—Table 1, PVNO level=0.05 wt. %     -   Example 4—Table 1, Control, PVNO level=0 wt. %

As is illustrated in Table 1, the tantalum to PETEOS selectivity was observed to increase from 1.5 to 24.6 with increasing PVNO level over the range 0-0.25 wt. % of PVNO. The tantalum to copper selectivity did not change appreciably with varying PVNO level over this range of 0-0.25 wt. %. TABLE 1 Effect of polyvinylpyridine-N-oxide on Tantalum to PETEOS selectivity Example 1 2 3 4 BA CS 5 5 5 5 NH₄F (wt. %) 0.22 0.22 0.22 0.22 S104E (wt. %) 0.07 0.07 0.07 0.07 CDX 2128 (wt. %) 0.1 0.1 0.1 0.1 PVNO (wt. %) 0.25 0.125 0.05 0 H₂O₂ (wt. %) 1.3 1.3 1.3 1.3 H₂O (Wt %) 92.56 92.68 92.76 92.81 pH (adjusted with 8 8 8 8 ammonia) Cu RR 2 psi (Å/min) 127 112 117 115 PETEOS RR 2 psi 20 130 279 341 (Å/min) Ta RR 2 psi (Å/min) 493 495 526 516 Ta: PETEOS Sel 2 psi 24.6 3.8 1.89 1.51 Ta: Cu Sel 2 psi 3.88 4.42 4.5 4.49

As the data shown in Table 1 indicates, tantalum to PETEOS selectivity increased from 1.51 to 24.6 as the concentration of PVNO increased in the formulation over the range 0-0.25 weight percent. The examples also demonstrate that tantalum to PETEOS selectivity can be tuned to any selectivity value desired over a broad range depending upon the concentration of PVNO in the formulation. 

1. A polishing composition comprising: a) an abrasive; and b) a polyvinylpyridine-N-oxide polymer.
 2. The polishing composition of claim 1 wherein the abrasive is a colloidal abrasive.
 3. The polishing composition of claim 1 further comprising c) an oxidizing agent.
 4. The polishing composition of claim 1 wherein the abrasive is silica.
 5. The polishing composition of claim 1 wherein the level of the polyvinylpyridine-N-oxide polymer in the composition ranges from 0.02 weight % to 1 weight %.
 6. The polishing composition of claim 5 wherein the level of the polyvinylpyridine-N-oxide polymer in the composition ranges from 0.05 weight % to 0.35 weight %.
 7. The polishing composition of claim 6 wherein the level of the polyvinylpyridine-N-oxide polymer in the composition ranges from 0.1 weight % to 0.35 weight %.
 8. A method of polishing comprising the steps of: A) placing a substrate in contact with a polishing pad; B) delivering a polishing composition comprising a) an abrasive; and b) a polyvinylpyridine-N-oxide polymer; and C) polishing the substrate with the polishing composition:
 9. The method of claim 8 wherein the abrasive is a colloidal abrasive.
 10. The method of claim 8 wherein the composition further comprises c) an oxidizing agent.
 11. The method of claim 8 wherein the abrasive is silica.
 12. The method of claim 8 wherein the level of the polyvinylpyridine-N-oxide polymer in the composition employed in the method ranges from 0.02 weight % to 1 weight %.
 13. The method of claim 12 wherein the level of the polyvinylpyridine-N-oxide polymer in the composition employed in the method ranges from 0.05 weight % to 0.35 weight %.
 14. The polishing composition of claim 13 wherein the level of the polyvinylpyridine-N-oxide polymer in the composition employed in the method ranges from 0.1 weight % to 0.35 weight %. 